Interstitial position of hydrogen in metals from entropy of solution

Abstract

The ion series Gex±, x=1–7, have been generated using direct laser vaporisation and detected using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Optimised non-local spin density approximation-density functional theory (NLSD) structures for these ions and their corresponding neutrals are presented. These results are used to interpret the relative intensity variation in positive-ion and negative-ion mass spectra and deduce the most prevalent neutral species in the laser plume. Ion–molecule reaction studies confirm the transitions to closed cyclic structures, as predicted by the NLSD calculations, at x=3 for the anions and x=4 for the cations. The ions most reactive towards CH3OH, CH3CH2OH, H2S and c-C3H6, were found to be the small cations with terminal, electron-rich (radical) Ge centres, while all the anions, with the exception of Ge2−, were essentially unreactive. The NLSD results reveal that there is little structural change upon either electron attachment or ionisation of the neutral structures. Small energy separations are predicted between the a3Πu and X3Σ−g states of Ge2 (6.2 kcal mol−1), the a3B1 and X1A1 spin states of Ge3 (4.6 kcal mol−1) and the singlet and triplet spin states of Ge5 (about 4 kcal mol−1 vertical separation). A Rydberg-like “square” quartet state of Ge4− was also discovered, 30 kcal mol−1 higher in energy than the lowest energy D2h doublet structure. NLSD did not locate minima corresponding to the anticipated 2Πu ground states of the mixed valence dimers Ge2+ and Ge2−, instead locating the states 4Σ+gGe+2 and 2Σ+gGe−2 both of which have electron vacancies below the HOMO. Collision induced dissociation (CID) results from FTICR-MS studies, and the recent literature laser photoelectron-zero electron kinetic energy (LPES–ZEKE) results for the anions Ge2− through to Ge7− were interpreted using the theoretical results from this study.